Photographic products, processes and compositions



wxewiz 35 0 I @MUQL zu- IH w IZ A IUTIZ l T Filed Dec. 19, 1963 ATTORNEYS 2 IEVENTORS BY M L J. F. DOWNEY ETAL PHO-TOGRAPHIC PRODUCTS, PROCESSES AND COMPOSITIONS Oct. 17, 1967 (3"IVOS 901) BONVG HOSSV United States Patent 3,347,672 PHOTOGRAPHIC PRODUCTS, PROCESSES AND COMPOSITIONS John F. Downey, Burlington, and Myron S. Simon, Newton Center, Mass., assignors to Polaroid Corporation, Cambridge, Mass, a corporation of Delaware Filed Dec. 19, 1963, Ser. No. 331,721 32 Claims. (Cl. 96-29) This invention relates to photography and more particularly to products, compositions and processes for the development of photosensitive silver halide elements.

It is one object of the present invention to provide novel processes and compositions for the development of silver halide emulsions, in which novel colored developing agents are used.

Another object is to provide novel processes and compositions for the development of silver halide emulsions, in which the novel developing agent is capable of developing an exposed silver halide emulsion and imparting a reversed or positive colored image of the developed image to a superposed image-receiving material.

A further object is to provide novel silver halide developing agents and novel products, processes and compositions suitable for use in preparing monochromatic and multichromatic photographic images.

Other objects of the invention will in part be obvious and will in part appear hereinafter.

The invention accordingly comprises the processes involving the several steps and the relation and order of one or more of such steps with respect to each of the others, and the products and compositions possessing the features, properties and the relation of elements which are exemplified in the following detailed disclosure, and the scope of the application of which will be indicated in the claims.

The objects of this invention may be accomplished by the use of certain novel dyes which have the ability to develop images present in an exposed silver halide emulsion; thus they may be referred to as dye developers. These novel dyes or dye developers will be further described hereinafter.

For a fuller understanding of the nature and objects of the invention, reference should be had to the following detailed description taken in connection with the accompanying drawing wherein:

FIGURE 1 is a graphic illustration comparing the spectrophotometric curves of the magneta dye developers of this invention with a prior class of magneta dye developers.

The photographic processes and compositions disclosed herein are particularly useful in the treatment of an exposed silver halide emulsion, whereby a positive dye image may be imparted to another element, herein referred to as an image-carrying or image-receiving element.

U.S. Patent No. 2,983,606, issued May 9, 1961 to Howard G. Rogers, discloses diffusion transfer processes wherein a photographic negative material, such as a photographic element comprising an exposed silver halide emulsion, is developed in the presence of a dye developer to impart to an image-receiving layer a reversed or positive dye image of the developed image by permeating into said emulsion a suitable liquid processing composition and bringing said emulsion into superposed relationship with an appropriate image-receiving layer. The inventive concepts herein set forth provide novel dye developers for use in such processes.

In carrying out the process of this invention, a photosensitive element containing a silver halide emulsion is expose-d and wetted with a liquid processing composition, for example by immersing, coating, spraying, flowing, etc., in the dark, and the photosensitive element superposed 3,347,672 Patented Oct. 17, 1967 prior to, during or after wetting, on an image-receiving element. In a preferred embodiment, the photosensitive element contains a layer of dye developer, and the liquid processing composition is applied to the photosensitive element in a uniform layer as the photosensitive element is brought into superposed position with an image-receiving element. The liquid processing composition permeates the emulsion to provide a solution of dye developer substantially uniformly distributed therein. As the exposed silver halide emulsion is developed, the oxidation product of the dye developer is immobilized or precipitated in situ with the developed silver, thereby providing an imagewise distribution of unoxidized dye developer dissolved in the liquid processing composition. This immobilization is apparently due, at least in part, to a change in the solubility characteristics of the dye developer upon oxidation, and especially as regards its solubility in alkaline solutions. It may also be due, in part, to a tanning effect on the emulsion by the oxidized developing agent. At least part of this imagewise distribution of unoxidized dye developer is transferred by irnbibition, to a superposed image-receiving layer. The image-receiving layer receives a depthwise diffusion, from the emulsion, of unoxidized dye developer, without appreciably disturbing the imagewise distribution thereof, to provide a reversed or positive, colored image of the developed or negative image. The image-receiving element may contain agents adapted to mordant or otherwise fix the difiused, unoxidized dye developer. Imbibition periods of approximately one minute have been found to give good results, but this contact period may be adjusted where necessary to compensate for variations in temperature or other conditions. The desired positive image is revealed by stripping the imagereceiving layer from the silver halide emulsion at the end of the imbibition period.

The dye developers of this invention may be utilized in the photosensitive element, for example in, on or behind the silver halide emulsion, or they may be utilized in the image-receiving element or in the liquid processing composition. In a preferred embodiment, a coating or layer of the dye developer is placed behind the silver halide emulsion, i.e., on the side of the emulsion adapted to be located most distant from the photographed subject when the emulsion is exposed and preferably also adapted to be most distant from the image-receiving layer when in superposed relationship therewith. Placing the dye developer behind the emulsion layer, as in the preferred embodiment, has the advantage of providing increased contrast in the positive image, and also minimizes any lightfiltering action by the colored dye developer. In this preferred embodiment, the layer of dye developer may be applied by using a coating solution containing about 0.5 to 8%, by weight, of the dye developer. Similar concentrations may be used if the dye developer is utilized as a component of the liquid processing composition. In an especially useful mode of disposing the dye developers in the photosensitive elements, the dye dveloper is dissolved in a water-immiscible solvent and then dispersed in a gelatin coating solution.

The liquid processing composition which is used in the processes herein disclosed comprises at least an aqueous solution of an alkaline compound, for example, diethylamine, sodium hydroxide or sodium carbonate, and may contain the dye developer. In some instances, it may contain an additional silver halide developing agent. If the liquid processing composition is to be applied to the emulsion by being spread thereon, preferably in a relatively thin, uniform layer, it may also include a viscosityincreasing compound constituting film-forming material of the type which, when spread over a water-absorbent base, will form a relatively firm and relatively stable film.

A preferred film-forming material is a high molecular Weight polymer such as a polymeric, Water-soluble ether inert to an alkali solution, as, for example, a hydroxyethyl cellulose or sodium carboxymethyl cellulose. Other filmforming materials or thickening agents whose ability to increase viscosity is substantially unaifected When left in solution for a long period of time may also be used.

The novel dye developers of this invention are anthraquinone dyes having the formula:

wherein each Z may be hydrogen, a hydroxy or an amino group; X and X are alkylene radicals which may be the same or different and are preferably lower alkylene radicals; and Y is a dihydroxyphenyl silver halide developing radical, e.g., p-dihydroxyphenyl, o-dihydroxyphenyl or halogen or alkyl substituted derivatives thereof.

In the preferred embodiment, X is an alkylene radical having 3 to 6 carbon atoms and X is an alkylene radical having 1 to 4 carbon atoms.

Alkylene radicals of greater length may be also employed, providing that the resulting dye developer is capable of beingdissolved in the liquid processing composition described herein and its oxidation product rendered immobile;

As examples of suitable dye developers Within the scope of Formula A, mention may be made of the following:

NHz OH (1) 1-aInino-2-(zeta-[methyl-2,5'-dihydroxy-hydrocinnnmido 1 -hexylan1ino) -4-hydroxy-anthraquinone lit (2) 1 nmino-2 ('v-[wethyl-2,5'-dihydroxy-hydrocinnamido] propylamino) 4-hydroxy anthraquinone (3) 1-amino-2-(v-[a-methy1-2' ,5-dihydroxy-hydrocinnamido] propylamino) -4-hydroxy-anthraquinone (4) l-amino-B- ('y-homogentisamido=propy1amino -4-hydr0xyanthraqumone II I O OH (6) 1-am1no-2-(zeta-[2' 5-dihydroxy-hydroclnnamido]- hexylamino) -4-l1ydroxy-anthraquinone (7) l-ztmino-2-(zeta-homogentisamido-hexylamino) '4- hydroxy-anthraquinone O NH: H l O CH (9) 1-amino-2-l( 'ya-methyl3' ,4 -dihydroxy-hydrocinnamido] propylztmino) 4-11ydr0xy-anthraquin0ne (10) 1, 5-diamino-2("y-la-methy1-2,5-dihydroxy-hydrocinnarmdo -pr0py1amino -4,8-dihydroxy-anthraquinone (11) 1-amino-2-(zeta[2,5-dihydroxy-hydroclnnamtdo]- hexylamino A-hydroxy-anthraquinone (12) 1-amin0-2 (zeta a-methy1-3,4'-dihydroxy-hydrocinnamido] -hexy1amino) -4-hydroxy-anthraquinone (13) 1,5-diamino-2-(zeta-[a-methyl-Z,5-dihydroxy-l1ydrocinnam1do]hexy1amino) -4,B-dihydroxy-anthraquinone (14) 1 amino-2(zeta-[3',4'-d1hydroxy-hydrocinnamido]- hexylamino) -4-hydroxy-anthraquinone The dye developers of this invention may be prepared by reacting an anthraquinone of the formula:

( (it NH,

n z OH wherein R is a suitable halogen, preferably bromine, or

a pheuoxy group, e.g.,

etc.; with a compound of the formula:

(C) N'H3-X-NH2 to form a compound of the formula: (D) z (I? IIIH:

NE-XNH2 Z ii) OH and thereafter reacting the compound of Formula D with a suitable derivative, e.g., the lactone, of an acid of the formula: (E) HOOCX Y O NH, II Ag)? OH l-amin0-2bromo-et-hydroxy-anthraquinone 1amino-2- (p-ehlorophenoxy) -4-hydroxyenthraquinone OH O NH:

I Y NH: O OH 2-chlor0-1,fi-diamin0-4,S-dihydroxy-unthr aquinone O NH:

H O OH 1-21min0-4-hydroxy-2-pheno-xy-anthraquinone As examples of useful compounds within the scope of Formula C, mention may be made of:

2( 2)s 2 Hexylene diamine z( 2)3 2 Trimethylene diamine Z( 2)4- 2 Tetramethylene diamine As examples of useful compounds within the scope of Formula E, mention may be made of:

Homogentisic acid pHydroxyhydrocinnamic acid a-methy12,5-dihydroxy-hydrocinnamic acid a-ethyl-2,5dihydroxy-hydrocinnamic acid HO -CH:COOH

3,4-dil1ydroxyphenylacetic acid 3,4-dihydroxyhydrocinnamic acid The following nonlimiting examples illustrate the preparation of novel dye developers within the scope of this invention:

Example 1 A solution containing 10 grams of 1-arnino-2-phenoxy- 4-hydroxy-anthraquinone in 100 cc. of hexylene diamine was heated on a steam bath for 3 hours, cooled, and poured into 2 liters of hexane. The resulting mixture was stirred forthree-quarters of an hour and filtered. The product was reslurried in hexane and filtered. The resulting filter cake was reslurried in water and filtered. This material from the water-washing was crystallized from methyl alcohol to yield 4.9 grams of l-amino-Z-(zetaamino-hexylamino) 4 hydroxy anthraquinone, which melted at 193-196 C., and had the following structural formula:

A mixture of 13.3 grams of l-amino-Z-(zeta-amino-hexylamino)-4-hydroxy-anthraquinone (prepared in the foregoing manner), 7.5 grams of a-ethyl-Z,5dihydroxy-hydrocinnarnic acid lactone and 1020 cc. of toluene was heated on a steam bath for 20 hours. The resulting product was filtered and washed with hot toluene. The dried filter cake gave 15.9 grams of l-amino-Z-(zeta-[ct-ethyl- 2,5-dihydroxy-hydrocinnamido]-hexylarnino) 4 hydroxy-anthraquinone,. which melted at 209-212 C.; had a spectral absorption curve with k at 528 and 565 m in methyl Cellosolve; 5 5:20,600 and e =20,- 000, and had the following structural formula:

Example 2 A mixture containing 30 cc. of 1,3-diamino-propane and 3 grams of 1-amino-2-phenoxy-4-hydroxy anthraquinone was heated on a steam bath for 20 minutes and then poured into four liters of water. The resulting precipitate when filtered and dried gave 2.2 grams of l-amino- 2-[y-amino propylamino] 4 hydroxy anthraquinone, which melted at 211213 C. on crystallization from methanol, and had the following structural formula:

l r NIL-(CH1) s-NH1 Example 3 A mixture of 1.0 gram of 1-amino-2-[-y-amino-propylamino]-4-hydroxy-anthraquinone (prepared as described in Example 2), 0.65 gram of a-methyl-2,54lihydroxyhydrocinnamic acid lactone and cc. of toluene was heated on a steam bathfor 20 hours. The resulting product was filtered and washed with toluene. The dried filter cake gave 1.2 grams of 1-amino-2-(- -[a-methyl-2,5'-hydroxy-hydrocinnamido] -propylamino) -4-hydroxy-anthraquinone, which melted at 225-228 C.; had a spectral absorption curve with A at 529 and 567 mp. in methyl Cellosolve; e =21,8()0 and e =20,800, and had the following structural formula:

Example 4 A mixture containing 2.0 grams of 1-amiu0-2-['yamino-propylamino]-4-hydroxy-anthraquinone (prepared as described in Example 2), 2.0 grams of homogentisic acid lactone and 200 cc. of methyl Cellosolve was heated on a steam bath for 20 hours under nitrogen. A deaerated solution of 2.0 grams of sodium hydroxide in 20 cc. of water was added to hydrolyze the excess lactone. Carbon dioxide was bubbled into the resulting mixture until neutral. The reaction mixture was poured into 2 liters of water. The resulting product was filtered OE and washed with water to yield 2.7 grams of l-amino-2 (v-homogentisamidopropylamino)-4 hydroxy anthraquinone, which melted at 187-l99 0.; had a spectral absorption curve with A at 527 and 565 mu in methyl Cellosolve; and had the following structural formula:

Example 5 A mixture containing 2.9 grams of 1-amino-2-(zeta-,

arnino-hexylamino)-4-hydroxy anthraquinone (prepared as described in Example 1), 2.0 grams of u-methyI-LS-dihydroxy-hydrocinnamic acid lactone and 200 cc. methyl Cellosolve was heated on a steam bath for 20 hours under nitrogen. A deaerated solutionof 2.0 grams of sodium hydroxide in 20 cc. of water was added to hydrolyze the excess lactone. Carbon dioxide was bubbled into the re-.

sulting mixture until neutral. The reaction mixture was poured into 2 liters of water. The resulting product was filtered off and washed with water to yield 2.1 grams of l-amino-Z-(zeta [m methyl 2',5 dihydroxy hydrocinnamido-hexylamino)-4-hydroxy-anthraquinone, which melted at l64 C., had a spectral absorption curve withx at 529 and 565 m in methyl Cellosolve; and had the following structural formula:

I Example 6 A mixture containing 2.0 grams of l-amino-2-(zetaamino-hexylamino) -4-hydroxy anthraquinone (prepared as described in Example 1), 2.0 grams of 2,5-dihydroxyhydrocinnamic acid lactone and 200 cc. of methylCellosolve was heated on a steam bath for 20 hours under nitrogen. A deaerated solution of 2.0 grams of sodium hydroxide in 20 cc. of water was added to hydrolyze the excess lactone. Carbon dioxide was bubbled into the resulting mixture until neutral. The reaction mixture was poured into 2 liters of water. The resulting product was filtered off and washed with water to yield 2.1 grams of l-amino-2-(zeta-[2,5'-dihydroxy-hydrocinnamido]-hexylamino) 4 hydroxy antbraquinone, which melted at 134-142 C.; had a spectral absorption curve with k at 527 and 565 Hill. in methyl Cellosolve; and had the following structural formula:

Example 7 A mixture containing 2.0 grams of 1-amino-2-(zetaamino-hexylamino)-4-hydroxy-anthraquinone (prepared as described in Example 1), 2.0 grams of homogentisic acid lactone and 200 cc. methyl Cellosolve was heated on a steam bath for 20 hours under nitrogen. A deaerated solution of 2.0 grams of sodium hydroxide in 20 cc. of Water was added to hydrolyze the excess lactone. Carbon dioxide was bubbled into the resulting mixture until new tral. The reaction mixture was poured into 2 liters of water. The resulting product was filtered oil and washed with water to yield 2.4 grams of l-amino-Z-(zeta-homogentisamido-hexylamino) -4-hydroxy-anthraquinone which melted at 134142' C., and had the following structural formula:

The following examples of the photographic utilization of the dye developers of this invention are given for purposes of illustration only.

Example 8 A photosensitive element was prepared by coating a gelatin subcoated film base at a speed of 10 feet/minute with a solution comprising 0.15 gram of 1-amino-2-(zeta- [or ethyl-2',5-dihydroxyhydrocinamido] hexylarnino)- 4-hydroxy-anthraquinone [Formula 1] dissolved in cc. of 2% cellulose acetate hydrogen phthalate in a 50:50 mixture, by volume, of acetone and tetrahydrofuran. After this coating dried, a green-sensitive silver iodobromide emulsion was coated on at a speed of 5 feet/minute and allowed to dry. This photosensitive element was exposed for 2 seconds and processed by spreading, between the thus exposed photosensitive element and a superposed image-receiving element, an aqueous processing composition comprising:

Water, cc. 100.00 KOH, gm. 11.20 Zinc nitrate, gm. 0.50 Hydroxyethyl cellulose (high viscosity) [commercially available from Hercules Powder Co.,

under the trade name of Natrosol 250], gm. 4.00 Benzotriazole, gm. 3.50 Sodium thiosulfate, gm 0.50 N-benzyl-oc-picolinium bromide, gm. 2.00

The image-receiving element was prepared in accordance with the disclosure of the copending application of Edwin H. Land, Serial No. 234,864, filed November 1, 1962 and comprised a layer of a 2:1 mixture, by weight, of polyvinyl alcohol and poly-4-vinylpyridine, a layer of polyvinyl alcohol, and a layer of a half-butyl ester of poly- (ethylene/rnaleic anhydride) coated on a baryta paper support. After an im'bibition period of approximately one minute, the image-receiving element was separated and contained a magenta positive transfer image.

Example 9 The procedure described in Example 8 was repeated, except that the dye developer was dispersed in a layer of gelatin. The coating solution from which the dye developer layer was coated was prepared by dissolving 0.40 gram of the dye developer in 0.50 cc. of N-n-butylacetanilide and 0.75 cc. of triethyl phosphate, and agitating this mixture in a Waring blender for one minute with a solution of 3.40 grams of 10% gelatin solution, 0.80 cc. of water, and 0.70 cc. of alkanol B. 4 cc. of the resulting dye dispersion was added to 9 cc. of water containing 2.00 cc. of 12% aqueous saponin, and then coated on the gelatin subcoated film base at a speed of 10 feet/minute. Exposure and processing in the manner described in Example 8 yielded a magenta positive transfer im-age.

Example 10 A photosensitive element was prepared by coating a gelatin subcoated film base at a speed of 10 feet/minute with a solution comprising 0.20 gram of l-amlI10-2-('y[0tethyl 2',5' dihydroxy hydrocinnamido] propylamino)-4-hydroxy-anthraquinone [Formula 2] dissolved in 5 cc. of 2% cellulose acetate hydrogen phthalate in a 50:50 mixture, by volume, of acetone and tetrahydrofuran. After this coating dried, a green-sensitive silver iodobromide emulsion was coated on at a speed of 5 feet/minute and allowed to dry. Exposure and processing in the manner described in Example 8 gave a magenta positive transfer image. 7 The addition of 0.2 gram of 4'-methy=lphenyl-hydroquinone to the processing solutions of Examples 8-10 gave comparable magenta images which had an appreciably lower D Substitution in the procedures described in Examples 8-10 of the other dye developers whose preparations are described above gave similar positive transfer images.

Prior to the present invention, it had not been thought possible to prepare compounds within the scope of Formula A. In other words, it was not thought possible by one skilled in the art that reacting a compound of Formula B with a compound of Formula C would produce an amino substituent placed ortho to the amino group on the 1-amino-4-hydroxy-anthraquinone nucleus of Formula D, since attempts to substitute an amino group in the 2-position of a 1,4-diamino-anthraquinone have been unsuccessful.

Where each Z of Formula A is hydrogen, the resulting compounds are magenta dye developers possessing excellent stability and spectral absorption characteristics. In photographic processes such as are described and claimed in the aforementioned U.S. Patent No. 2,983,606, particularly in such processes for preparing multicolor images, it is extremely desirable that the dye developers employed possess the desired spectral absorption characteristics, as well as being stable to light, heat and humidity, so as to provide a stable image of the desired color. As is frequently the case, a magenta dye of the proper color, e.g., having the proper blue transmission, may not possess the desired stability. Conversely, magenta dyes having good light stability frequently are not of the proper color, especially for use in multicolor processes. 'Ihe magenta dye developers of the present invention are of particular value in that they are both highly stable and exhibit excellent color for use in preparing color images, particularly multicolor images where optimum color reproduction is desired.

Thus, while the magenta dye developers of this invention are neither the most stable heretofore known nor do they possess the most optimum spectral absorption characteristics, they are unusual in that they combine these properties to a high degree so as to provide magenta dye developers extremely useful in the aforementioned photographic processes and products, particularly in such products and processes for preparing multicolor images.

As shown in FIGURE 1, the spectrophotometric curve of a typical magenta dye developer of this invention,

specifically 1 amino 2 (zeta [c ethyl 2',5' dihydroxy hydrocinnamido] hexylamino) 4 hydroxyanthraquinone, (solid line) is compared with a typical 2-alkoxy-1,4-diamino-anthraquinone magenta dye developer of the prior art, specifically l,4-diam1no-2-(e-[ 2',5'- dihydroxy hydrocinnamidolpentoxy) anthraqulnone (dotted line), the solvent in each case being methyl Cellosolve. The last-named dye developer and analogous 2- alkoxy-anthraquinone .dye developers are described and claimed in the copending application of John F. Downey and Myron S. Simon, Serial No. 152,014, filed November 13, 1961, now Patent No. 3,245,790.

While only a single species of each class of dye developer has been shown for purposes of comparison, it will be understood that the various species of the chromophoric systems illustrated in the drawing have substantially identical curves.

It will be observed that the k of the dye developers of this invention are shifted more towards the voilet or a lower wavelength in the visible spectrum, and they have less absorption in the red region and more absorption in the green region of the spectrum. More specifically, the dye developer of this invention (solid line) has a spectral absorption curve with k at 528 and 565 mm; 6 20,600 and e {=20,000; while the prior Z-alkoxy dye developer (dotted line) has a spectral absorption curve with X at and m/L; 6534=16,300; 572 17,400.

The difference in spectral absorption characteristics illustrated in the graph permits themagenta dye developers of this invention to afford more desirable color balance or accuracy of color reproduction in multicolor. images prepared in the manner heretofore described.

The dye developers of this invention are also useful.

in integral multilayer photosensitive elements for use in multicolor diffusion transfer processes. As an example of such photosensitive elements, mentionmay be made of the photosensitive elements disclosed and claimed in the copending US. application of Edwin H. Land and Howard G. Rogers, Serial No. 565,135, filed Feb. 13, 1956, wherein at least two selectively sensitized photosensitive strata are superposed on a single support andare processed, simultaneously and without separation, with a single common image-receiving element. A suitable arrangement of this type comprises a support carrying a red-sensitive silver halide emulsion stratum, a greensensitive silver halide emulsion stratum and a blue-sensitive silver halide emulsion stratum, said emulsions having associated therewith, respectively, a cyan dye developer, a magenta dye developer and a yellow dye developer. In one of the preferred embodiments of photosensitive elements of this type, the dye developers are disposed in separate alkali-permeable layers behind the photosensitive silver halide emulsion stratum with which they are associated.

The photosensitive elements within the scope of this invention may be used in film units which contain a plurality of photosensitive frames. The photosensitive elements of this invention are especially useful in composite roll film and film pack structures intended for use in a Polaroid Land Camera, sold by Polaroid Corporation, Cambridge 39, Massachusetts, or a similar camera structure such, for example, as the roll film type camera forming the subject matter of U.S. PatentNo. 2,435,717, issued to Edwin H.. Land on Feb. 10, 1948, or the film pack camera structure shown in US. Patent No. 2,991,702 issued to Vaito K. Eloranta on July 11, 1961. In general, such composite roll films comprise a photosensitive roll, a roll of image-receiving material and a plurality of pods 12 containing an aqueous alkaline processing solution. The rolls and pods are so associated with each other that, upon processing, the photosensitive element may be super-v posed on the image-receiving element and the pods may be ruptured to spread the aqueous alkaline processing solution between the superposed elements. The nature and.

construction of the pods used in such units are well known to the art. See, for example, US. Patents Nos. 2,543,181 and 2,634,886, issued to Edwin H. Land.

It will be noted that the liquid processing composition may contain one or more auxiliary or accelerating silver halide developing agents, such as p-methylarninophenol (Metol); 2,4-diaminophen0l (Amidol); benzylaminophe-.

nol; hydroquinone; a substituted hydroquinone such as toluhydroquinone, phenyl-hydroquinone, or 4-methylphenylhydroquinone; or a 3-pyrazolidone such as l-phenyl-3- pyrazolidone. These silver halide developing agents are substantially colorless, at least in their unoxidized form. It is possible that some of thedye developer oxidized in exposed areas may be oxidized by an energy transfer reaction with oxidized auxiliary developing agent.

In addition, development maybe effected in the presence of an onium compound, particularly a quaternary ammonium compound, in accordance with the. processes disclosed and claimed in the copending application of Milton Green and Howard G. Rogers, Serial No. 50,851, filed August 22, 1960, now Patent No. 3,173,786.

The dye developers of this invention may be used also in conventional photographic processes, such as tray or tank development of conventional. photosensitive .films, plates or papers to obtain black-and-white, monochromatic or toned prints or negatives. By way of example, a developer composition suitable for such use may comprise an aqueous solution of approximately 1-2% of the dye developer, 1% sodium hydroxide, 2% sodium sulfite and 0.05% potassium bromide. After development is completed, any unreacted dye developer is washed out of the photosensitive element, preferably with an alkaline Washing medium or other medium in which the unreacted dye developer is soluble. The expression toned" is used to designate photographic images wherein the silver is retained with theprecipitated dye, whereas monochromatic is intended to designate dye images free of silver.

It should be noted that the dye developers of this medium are self-sufficient to provide the desired color image and do not depend upon coupling reactions to produce the desired color. They thus provide a complete departure from conventional photographic color processes in which the color is produced by a coupling reaction between a color former or coupler and the oxidized developing agent, as well as so-called auto-coupling processes in which color is obtained by a reaction of the oxidized developing agent with unoxidized developing agent.

Itwill be apparent that, by appropriate selection of the image-receiving element from among suitable known opaque and transparent materials, it is possible to obtain either a colored positive reflection print or a colored positive transparency. Likewise, the inventive concepts herein set forth are adaptable for multicolor work by the use of special photographic materials, for example, film materials of the type containing two or more photosensitized 'ele ments associated with an appropriate number of imagereceiving elements and adapted to be treated with one or more liquid processing compositions, appropriate dye developers suitable to impart the desired subtractive colors being incorporated in the photosensitized elements or in the liquid processing compositions. Examples of such photographic materials are disclosed in US. Patent No. 2,647,049 to Edwin H. Laud.

As examples of useful image-receiving materials, mention may be made of nylon, e.g., N-methoxyrnethyl-polyhexamethylene adipamide, polyvinyl alcohol, and gelatin,

13 pending application of Howard G. Rogers and Harriet W. Lutes, Serial No. 50,849, filed August 22, 1960, now Patent No. 3,265,498.

The dye developers herein set forth are also useful in the formation of colored images in accordance with the photographic products and processes described and claimed in US. Patent No. 2,968,554, issued to Edwin H. Land on January 17, 1961.

The novel compounds herein disclosed are also suitable for use as dyes for textile fibres, such as nylon.

In the preceding portions of the specification, the expression color has been frequently used. This expression is intended to include the use of a plurality of colors to obtain black.

Since certain changes may be made in the above products, compositions and processes without departing from the scope of the invention herein involved, it is intended that all matter contained in the above description or shown in the accompanying drawing shall be interpreted as illustrative and not in a limiting sense.

What is claimed is:

1. A novel photographic developer composition comprising an aqueous alkaline solution of a silver halide auxiliary developing agent and an anthraquinone dye of the formula:

Z O NH2 I II I Z 0H wherein each Z is selected from the group consisting of hydrogen, hydroxy and amino groups; X and X are lower alkylene radicals; and Y is a dihydroxyphenyl silver halide developing radical.

2. A novel photographic developer composition comprising an aqueous alkaline solution of a silver halide auxiliary developing agent and l-amino-Z-(zeta-[et-ethyl- 2',5' dihydroxy hydrocinnamido] hexylamino) -4-hydroxy-anthraquinone.

3. A novel photographic developer composition comprising an aqueous alkaline solution of a silver halide auxiliary developing agent and l-amino-Z-(y-[a-methyl-2,5- dihydroxy hydrocinnamido] propylamino)-4-hydroxyanthraquinone.

4. A novel photographic developer composition comprising an aqueous alkaline solution of a silver halide auxiliary developing agent and 1-amino-2-('y-[ot-methyl- 2',5'-dihydroxy hydrocinnamido] propylamino) 4-hydroxy-anthraquinone.

5. A novel photographic developer composition comprising an aqueous alkaline solution of a silver halide auxiliary developing agent and l-amino-Z-(y-homogentisamido-propylamino)-4-hydroxy-anthraquinone.

6. A novel photographic developer composition comprising an aqueous alkaline solution of a silver halide auxiliary developing agent and l-amino-Z-(zeta-[a-methyl- 2,5 dihydroxy hydrocinnamido] hexylamino)-4-hydroxy-anthraquinone.

7. A novel photographic developer composition comprising an aqueous alkaline solution of a silver halide auxiliary developing agent and 1-amino-2-(zeta-[2,5-dihydroxy hydrocinnamido] hexylamino)-4-hydroxy-anthraquinone.

8. A novel photographic developer composition comprising an aqueous alkaline solution of a silver halide auxiliary developing agent and 1-amino-2-(zeta-homogentisamido-hexylamino -4-hydroxy-anthraquinone.

9. A novel photographic product comprising a support, a silver halide emulsion in a layer on said support, and a dye developer in a layer on the same side of said sup- Z O NH:

Z O OH wherein each Z is selected from the group consisting of hydrogen, hydroxy and amino groups; X and X are lower alkylene radicals; and Y is a dihydroxyphenyl silver halide developing radical.

10. A novel photographic product comprising a support, a silver halide emulsion in a layer on said support, and 1 amino 2-(zeta-[a-ethyl-2',5'-dihydroxy-hyd-rocinnamido]-hexylamino) 4 hydroxy anthraquinone, in a layer on the same side of said support as said emulsion.

11. A novel photographic product comprising a support, a silver halide emulsion in a layer on said support, and l-amino-Z-(y-[a-ethyl-2,5'-dihydroxy hydrocinnamido] -propylamino)-4-hydroxy-anthraquinone in a layer on the same side of said support as said emulsion.

12. A novel photographic product comprising a support, a silver halide emulsion in a layer on said support, and 1-arnino-2-('y-[a-methyl-2',5 dihydroxy hydrocinnamido] -propylamino) 4 hydroxy anthraquinone in a layer on the same side of said support as said emulsion.

13. A novel photographic product comprising a support, a silver halide emulsion in a layer on said support, and 1 amino 2 ('y homogentisamido-propylamino)-4-hydroxy-anthraquinone in a layer on the same side of said support as said emulsion.

14. A novel photographic product comprising a sup port, a silver halide emulsion in a layer on said support, and l amino 2 (zeta-[u-methyl-2',5-dihydroxy-hydrocinnamido] -hexylamino)-4-hydroxy anthraquinone in a layer on the same side of said support as said emulsion.

15. A novel photographic product comprising a support, a silver halide emulsion in a layer on said support, and 1 amino-2-(zeta-[2',5'-dihydroxy-hydrocinnamido]- hexylamino)-4-hydroxy-anthraquinone in a layer on the same side of said support as said emulsion.

16. A novel photographic product comprising a support, a silver halide emulsion in a layer on said support, and 1-amino-2-(zeta-homogentisamido-hexylamino) 4- hydroxy-anthraquinone in a layer on the same side of said support as said emulsion.

17. In a process of forming a photographic image in color, the steps which comprise contacting an exposed silver halide emulsion with an aqueous alkaline solution containing an anthraquinone dye developer of the formula:

I H z 0 011 wherein each Z is selected from the group consisting of hydrogen, hydroxy and amino groups; X and X are alkylene radicals; and Y is a dihydroxyphenyl silver halide developing radical; oxidizing said dye developer in developed areas to provide in said emulsion a predetermined distribution of unoxidized dye developer and transferring at least part of said distribution of said unoxidized dye developer by imbibition from said emulsion to an imagereceiving element in superposed relationship with said emulsion to impart to said image-receiving element a positive dye image.

18. A process as defined in claim 17 wherein said dye developer is 1 amino-Z-(zeta-[a-ethyl-2,5'-dihydroxyhydrocinnamido] -hexylamino -4-hydroxy-anthraquinone.

19. A process as defined in claim 17 wherein said dye developer is l-amino 2 ('y-[aethyl-2,5'-dihydroxyhydrocinnamido]-propylamino) 4 hydroxy-anthraquinone.

20. A process as defined in claim 17 wherein said dye developer is l-amino 2 -[a-methyl-Z,5-dihydroxyhydrocinnamido]-propylamino) 4 hydroxy-anthraquinone.

21. A process as defined in claim 17 wherein said dye developer is 1 amino-2-('y-homogentisamido-propylarnino)-4-hydroxy-anthraquinone.

22. A process as defined in claim 17 wherein said dye developer is 1-amino2-(zeta-[a-methyl-Z,5-dihydroxyhydrocinnamido] -hexylamino -4-hydroxy-anthraquinone.

23. A process as defined in claim 17 wherein said dye developer is 1 amino2-(zeta-[2,5 dihydroxy-hydrocinnamido]-hexylarnino) 4 hydroxy-anthraquinone.

24. A process as defined in claim 17 wherein said dye developer is l-arnino 2 (zeta-homogentisamido-hexylamino) -4-hydroxy-anthraquinone.

25. A photographic process which comprises exposing a light-sensitive silver halide emulsion and contacting said exposed silver halide emulsion with an aqueous alkaline solution containing an anthraquinone dye of the formula:

wherein each Z is selected from the group consisting of 16- developer is 1 amino 2 (zeta-[a-ethyl-2',5'-dihydroxyhydrocinnamido]-hexylamino) 4 hydroXy-anthraquinone.

27. A process as defined in claim 25 wherein said dye developer is 1 amino-2-( -[ix-ethyl-(2,5-dihydroxy)- hydrocinnamido]-propylarnino) 4 hydroxyanthraquinone.

28. A process as defined in claim 25 wherein said dye developer is I-aminO-Z-(y-[a-methyl Z',5-dihydroxyhydrocinnamido]--propylamino) 4 hydroxy-anthraquinone.

29. A process as defined in claim 25 wherein said dye developer is l-arnino 2 ('y-homogentisamido-propyl:

amino) -4-hydroXy-anthraquinone.

30. A process as defined in claim 25 wherein said dye developer is l-arnino 2 (Zeta-[a-methyl-2,5-dihy-.

droxy-hydrocinnamido]-hexylamino) 4 hydroxy-anthraquinone.

31. A process as defined in claim 25 wherein said dye developer is 1 amino-Z-(zeta-[2',5'-dihydroXy-hydrocinnamido] -hexylamino -4-hydroxy anthraquinone.

32. A process as defined in claim 25 wherein said dye developer is 1 amino-2-(zeta-homogentisamido-hexylamino) -4-hydroxy-anthraquinone.

References Cited UNITED STATES PATENTS 5/1961 Rogers 96-29 6/1966 Blout 9629 OTHER REFERENCES NORMAN G. TORCHIN, Primary Examiner.

J. TRAVIS BROWN, Examiner. 

17. IN A PROCESS OF FORMING A PHOTOGRAPHIC IMAGE IN COLOR, THE STEPS WHICH COMPRISE CONTACTING AN EXPOSED SILVER HALIDE EMULSION WITH AN AQUEOUS SOLUTION CONTAINING AN ANTHRAQUINONE DYE DEVELOPER OF THE FORMULA: 